For the case where a practitioner has different hours on the same day for different services, they can be set on the service.
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An example would be a practitioner provides Adult services in the morning and Pediatric services in the afternoon.
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On a service, click the "New Service Practitioner" button

Next to User, Click the "Lookup" button to select the practitioner

Next to Business Hours, Click the "Lookup" button to select the Business Hour

Click Save